Process for the treatment of abietyl compounds and products produced thereby



60 alumina.

Patented Sept. 20, 1938 PROCESS FOR THE TBEA OF ABIE- TBIENT TYLCOMPOUNDS PROD CTS PRO- DUOED THEREBY Edwin n. Littmann, Wilmington.n.1, aasilnor to Hercules Powder Company, Wilmington, Del., acorporation of Delaware No Drawing.

Original application June 12, 1936, Serial N0. 84,877. Divided and thisapplication September 9, 1936, Serial N 100.039 20 Claims. (CL flit-103)This invention relates to a process for the treatment of rosin, rosinacids, and compounds derived from rosin which contain the hydrocarbonnucleus characteristic of rosin acids, and to the products thereof. Morespecifically, this invention relates to the treatment of such compounds,

so as to decrease their unsaturated characteristics, and to the productsresulting from such treatment. a This treatment in accordance'with thisinvention comprises essentially contacting rosin, a rosin acid, or othercompound containing the hydrocarbon nucleus of a rosin acid with acatalyst of the type hereinafter described, in a man- 5 ner to excludethe possibility of reaction between the rosin or rosin derivative andany added material capable of reducing the unsaturation or the rosinacid nucleus. As a result of such treatment a change in the chemical andphysi- 20 cal properties of the rosin or rosin derivative takes place,and the resultant product will be found to have a greatly decreasedunsaturation. In many cases, the product will also be found to have ahigher melting point and improved prop 25 erties. These changes in thephysical and chemical characteristics of the material are believed to bedue to an intraand inter-molecular rearrangement of the hydrogen atomsocc therein, with no change in the carbon skeleton. 30 The catalystswhich may be used in enacting this change are those which catalyze thehydrogenation of unsaturated organic compounds, as,

for example, nickel, copper chromite, platinum.

palladium, etc. While both base and noble metal 35 hydrogenationcatalysts are useful in producingthis change or intraand inter-molecularrearrangement, a catalyst of noble metal supported on an inert carrieris particularly eflective.

Palladium in an amount within the range of about .4 1% to about 25%supported on an inert carrier.

such as, for example, granular alumina or fibrous asbestos, ispreferred.

A novel type of palladium catalyst, devised especially for the processin accordance with this i5 invention, may be made as follows:

A solution containing 1 part by weight of palladium chloride, 2 partsby.weight of concentrated hydrochloric acid and 8 parts by weight 01'water is adsorbed on parts by weight of graniuar This mixture is thentreated with 2 parts by weight of an approximately 37% formaldehydesolution, followed with approximately 15 parts by weight of anapproximately 10% sodium hydroxide solution, enough to make the solutionslightly alkaline and precipitate the pali3 ladium black. .Afterthorough agitatiom the mixture is filtered, washed with water, diluteacetic acid, and then again with water, until'neutral. The product isthen finally dried in an oven at 80 C. to 100 C. This catalyst is mostit) emcient in the treatment in accordance with this invention and itsuse is preferred.

Rosin is a mixture of isomeric rosin acids having the formula CuHzoCOOH,in which the group CnHa has been shown to contain two double l6 bondsand to possess an alkylated phenanthrene nucleus- It will be understoodthat when reference is made herein to a rosin acid, a carboxylic acidround in rosin and containing the group CuHa, is meant. More than fiftydifierent isomeric rosin acids have been reported in the literature. Thebest known of these acids are abietic acid. sapinic acid and d-pimaricacid. The relative proportions in which these and the other isomericrosin acids occur in a given sample oi rosin depends on the source ofthe rosin. Thus, wood rosin contains more abietic acid than any of theother acids, while American gum rosin contains more sapinic acid. Frenchgum rosin con- 7 tains more d-pimaric acid. I

The hydrocarbon nucleus of each of these isomeric acids is capable ofreaction in accordance with this invention. and for the purposes oi thisinvention they are entirely equivalent. Thus,

for example, any of the various grades of American wood rosin, Americangum rofln,,French sum rosin, Portuguese gum rosin, Spanish gum rosinetc., may be treated to reduce their unsaturated characteristic. Theseveral isomeric acids found in various types or rosin, for example, 4abietic acid, d-pimaric acid, sapinic acid, etc., may be separated andtreated in purified form if. desired. Likewise, compounds derived'iromrosin or the rosin acids without alteration: of. the Ciel-la nucleus areequivalent to the rosin or rosin acids for the purposes of thisinvention. Further partially hydrogenated rosins and compoundscontaining a partially hydrogenatedhydrocarbon nucleus of a resin acidare still further reduced in unsaturation when treated by\'the processin phatic,

ether, pimaryl bornyl ether, sapinyl methyl ether, sapinyl ethyl ether,

accordance with this invention and are likewise equivalent to theunhydrogenated compounds from the standpoint of this invention. Suchcompounds are characterized by containing somewhere in theirstructurethe hydrocarbon group C19H31 containing one double bond, andare present in any hydrogenated rosin or rosin acid,

less than saturated with hydrogen, to an extent determined largely bythe degree of saturation.

The class of compounds which may be treated in accordance with theprocess of this invention to decrease their unsaturation and improvetheir properties are characterized by containing somewhere in theirstructure an alkylated phenanthrene group containing two double bondsand having the formula CroHzo or a partially hydrogenated phenanthrenegroup containing one double bond and having the formula ClOHM. Nogeneric term has developed in the literature to cover this closelyrelated group of compounds, so for convenience I will term them "Rosinyicompounds. The term "Rosinyl compound will hereinafter be understood toinclude the abietyl compounds, the similar groups of compounds derivedfrom rosin acids isomeric with abietic acid,partially hydrogenatedabietyl compounds, compounds derived from rosin acids isomeric withabietic acid. This term is not intended to include rosins or compoundsderived from rosins which have been hydrogenated sufficiently to removeboth double bonds or to include compounds derived from rosin by aprocess which materially alters the hydrocarbon skeleton of the, resinacid.

In addition to the various rosins, rosin acids. partially hydrogenatedrosins, and partially hydrogenated rosin acids mentioned hereinbefore,there are many other "RosinyP compounds which may be treated inaccordance with this invention. Thus, for example, I may treat themonohydric and polyhydric alcohol esters of rosins,ro'sin acids,partially hydrogenated rosins or partially hydrogenated rosin acids,such as, for example, their esters with methanol, ethanol, propanol,iso-propanol, butanol, iso-butanol, oleyl alcohol, lauryl alcohol,abietyl alcohol, hydroabietyl alcohol, furfuryl alcohol,tetra-hydrofurfuryl alcohol, ethylene glycol, diethylene slycol,triethylene glycol,. glycerol, erytheritol, pentaerytherol, sorbitol,mannitol, mixtures thereof,

phenol, etc. I may treat alcohols produced from resins and rosin acids,partially hydrogenated rosins, or partially hydrogenated rosin acids, bythe reduction of the carboxyl groups of the rosin acids, such as, forexample, abietyl alcohol, dihydroabietyl alcohol, sapinyl alcohol,dihydrosapinyl alcohol, pimaryl alcohol, dihydropimaryl alcohol, etc.Again, I may treat others formed by the etheriflcation of the alcoholsderived from rosins, rosin acids, partially hydrogenated rosins, andpartially hydrogenated rosin acids with allaromatic, or such as, forexample, abietyl methyl ether, abietyl ethyl ether, abietyl butyl ether,abietyl phenyl ether, abietyl bornyl ether, abietyl ter pinyl ether,pimaryl methyl ether, pimaryl ethyl ether, pimaryl propyl ether, pimarylphenyl ether,

., sapinyl propyl ether, sapinyl butyl ether, sapinyl phenyl ether,sapinyl bomyl ether, sapinyl terpinyl ether, etc. Likewise, I may treathydrocarbons produced by the decarboxylation ,of

and the similar partially hydrogenated hydroaromatic alcohols,

pimaryl terpinyl.

rosins, rosin acids, partially hydrogenated rosins.

' partially hydrogenated rosin acids, etc., such as,

for example, those produced by the treatment of rosins, rosin acids,partially hydrogenated rosins and .partially hydrogenated rosin acidswith a catalyst, as, p-toluene sulphonic acid, at an elevatedtemperature, according to the process disclosed in U. S. Patent1,975,211 to Alan C. Johnston, or by treatment with fuller's earth at anelevated temperature.

Compounds which contain in their structure a rosin acid nucleus orpartially hydrogenated rosin acid nucleus which has undergone theintraand inter-molecular rearrangementproduced by the process inaccordance with this invention, will hereinafter be referred to asl-lyex" compounds. The catalytic reaction by which the unsaturation ofthe rosin acid nucleus or the partially hydrogenated rosin acid nucleusis reduced will be termed the Hyex reaction".

In carrying out the process in accordance with this invention, theRosinyP' compound will be broughtinto contact with a hydrogenationcatalyst, preferably ,at an elevated temperature in order that apractical reaction rate may be obtained; however, the use of an elevatedtemperature is not necessary for the accomplishment of the desiredresult. The optimum temperature range for most satisfactory results isfrom about C. to about 250 C., and atemperature of about 220 C. to about250 C. is preferred. Pressure has littleor no effect on the reaction,which may be carried out in vacuo or at superatmospheric pressure ifdesired. Since atmospheric pressure is most convenient from an apparatusstandpoint, such will usually be used.

As thorough contact between catalyst and rosin or rosin acid can best beobtained when the "Rosinyl compound or partially hydrogenated Rosinyl"compound is in liquid or vapor certain circumstances it is desirable tocarry out the reaction in the vapor phase, ordinarily I prefer to carryit out with a liquid phase. The Rosinyl compound or the partiallyhydrogenated "Rosinyl compound may be in the molten condition or may, ifdesired, be dissolved in a suitable inert, non-reactive solvent, and thesolution so formed treated with a. hydrogenation catalyst. Anysolventfor the compound treated which is not a poison to a hydrogenationcatalyst and which does not contain catalyst poisons as impurities andwhich does not enter into the Hyex" reaction is suitable for thispurpose. Thus, for example, aliphatic hydrocarbons, the variouspetroleum fractions, monocyclic aromatic hydrocarbons, hydrogenatedaromatic hydrocarbons, etc., are suitable for the purpose. The aliphatichydrocarbons and the various petroleum fractions are particularlyuseful.

In accordance with this invention it is essential that the treatment of'the Rosinyl compound be carried out in such a manner that no reactioncan occur between the compound being treated and any addedmaterial/capable of reducing its unsaturation under the conditions ofreaction, In other words, any material which, under the conditions oftreatment, will react lift action with the compound which do not reduceits unsaturation, may be present. Thus, inert solvents, inertsases,etc., may be present. While the treatment may be carried out in thepresence of air, it is preferable to treat the Rosinyl "compound or thepartially hydrogenated Rosin compound in an atmosphere of a more inertgas, as, for example, carbon dioxide, nitro- 'be distilled under tionfrom the catalytically- -treated gen, etc.

The treatment in accordance with this invention may be carried outsimultaneously with other reactions, which do not involve a change inthe unsaturated characteristic of the rosin nucleus. Thus, rosin or arosin acid may be treated with a hydrogenation catalyst to produce anintraand inter-molecular rearrangement of the nucleus and, for example,simultaneously esterifled with an alcohol, to produce a rosin ester ofreduced unsaturation.

Contact between the RosinyP' compound or the partially hydrogenatedRosinyl compound and the catalyst should be maintained for from a fewseconds to hours or more, depending upon the temperature and upon theamount and activity of the catalyst employed. Upon the completion of thetreatment, the resultant product may be easily separated from thecatalyst by filtration. The product secured after the removal of thecatalyst, if volatile, may if desired,

reduced pressure and separated into two or more fractions. Where a highmelting point product is desired, such may be secured by the removal ofthe low-boiling fracmaterial.

' The product, in accordance with this invention, may be produced by oneor more of the three a1- ternate embodiments of the method in accordancewith this invention. By the first of these poisoning the hydrogenationcatalyst.

alternate embodiments the corresponding Rosinyl compound may' betreated, either alone or in solution, with a suitable catalyst toproduce the Hyex reaction; as described hereinbefore. 'This' embodimentwill be most advantageous for the'treatment of rosin compounds which arefree from impurities which will poison the catalyst.

or which are not of such nature that they act as catalyst poisons.

Thus, rosin may be contacted with a catalyst to produce a Hyex rosin, ora rosin ester may be passed over a catalyst to produce a Hyex" rosinester.

By a second embodiment oi the method in accordance with this invention aRosinyl compound may be treated with a suitable catalyst to produce the"Hyex" reaction, and simultaneously reacted, either alone or in thepresence 01' a sol vent, with some other material which is incapable ofaffecting the unsaturation of the rosin acid or partially hydrogenatedrosin acid nucleus or of Thus, a may be elevated mixture of wood rosinand methanol treated with a suitable catalyst at an temperature andpressure to produce a methyl abietate, which is identical in propertieswith the product secured bysubjecting methyl abietate to the fHyex'.reaction.

By a third embodiment of the method in accordance with this invention a"Rosinyl com pound may be treated, either alone or in solution, withasuitable catalyst to produce the Hyex reaction and the product so formedreacted with another material to produce the desired product. Thus, forexample, any of the different rosins may be contacted with a suitablecatalyst, as hereinbefore described to produce a "Hyex rosin, and thenesterifled by reaction with an alcohol to produce the "Hyex rosin esterand the Hyex" rosin ester so produced will be identical in propertieswith the Hyex" rosin ester produced according to the first or secondembodiments of my invention.

A wide variety of Hyex" compounds may be prepared by this embodiment ofmy invention. Thus, any one of the rosins, rosin acids or partiallyhydrogenated rosins mentioned above may be subjected to the Hyexreaction, and then decarboxylated as, for example, by'heating in contactwith fuller's earth or a sulphonic acid catalyst to produce a Hyex rosinoil. A' rosin or rosin ester may be subjected to Hyex treatment and thenreduced to the corresponding alcohol, as for example, by hydrogenationof the acid, or reduction of the ester with sodium and alcohol. Thealcohol so produced may then be etherified with another alcohol, suchas, for example, one of the aliphatic, aromatic, or hydroaromaticalcohols mentioned hereinbefore. A!- ternately, a rosin acid may bereduced to the corresponding alcohol, as for example, by catalytictreatment with hydrogen and the product subjected to the Hyex" reactionand then etherifled.

This third embodiment of my invention is particularly useful for theproduction of compounds which cannot be easily produced by the first orsecond alternative methods, due to the corresponding Rosinyl compound orpartially hydrogenated "Rosinyl compound being of a nature such that itacts as a poison to the catalyst in the Hyex reaction. Thus, forexample, many of the metallic salts of rosin acids or partiallyhydrogenated rosin acids have a tendency to poison the catalyst or tocontain catalyst. poisons unless proper precautionary measures are takenand, hence, cause diflipulty in the Hyex reaction. Hyex rosin salts,however, may be readily prepared by subjecting a rosin acid or apartially hydrogenated rosin acid to the Hyex" reaction and then formingthe salt of the Hyex rosin acid produced. ,Thus, any one of the rosins,rosin acids, or partially hydrogenated rosins mentioned above may besubiected to the "Hyex reaction and then reacted with a metallichydroxide or other metallic compound, capable of forming a metallic saltwith the "I-Iyex rosin acid. fI'hus, the "Hyex rosin acid may be reactedwith an alkali metal hydroxide, for example, sodium or potassiumhydroxide, to produce the corresponding alkali metal salt of the Hyexrosin with a heavy metal oxide or hydroxide, as for example, lead,cobalt, or manganese hydroxide, to produce the corresponding heavy metalsalts.-

The product in accordance with this invention, is a compound whichcontains somewhere in its structure a hydrocarbon group derived from anisomeric rosin acid, which has undergone what appears to be an intraandinter-molecular rearrangement to eliminate its unsaturation as measuredby the Wijis iodine value or the thiocyanate value. Such compounds may.for example, be of one of the following types: carboxylic acid, ester,alcohol, ether, hydrocarbon, metallic salt, etc. These compounds will befound to resemble, in general physical appearance, the compounds whichhave not been treated by the method in accordance with this invention,although frequently they are lighter in color and have a higher meltingpoint than the correin regard to their chemical unsaturation.

Due to the substantially saturated character of the products preparedinaccordance with this invention, their use will be found to be highlyadvantageous in many products in which untreated Rosinyl compounds arenow used. Thu.s-Hyex" rosin, Hyex rosin acids, Hyex rosin ethers, etc.will be found advantageous for use in paints, varnishes and lacquers, inplace of the corresponding Rosinyl compounds which have been example,those containing manganese, cobalt.

zinc, lead, etc., are particularly useful as driers in paints andvarnishes, since solutions: containing such driers remain bright and ofconstant drying strength on aging.

The carboxylic acids included within the scope A of this invention arethe isomeric rosin acids, or

. catalyst or any other commercial mixtures thereof in the various typesof rosins, mentioned hereinbefore, which have been subjected to theHyex" treatment. The

esters, in accordance with this invention, are compounds having thefollowing formula:

R-COO-A in which R is a hydrocarbon nucelus of one of the isomeric rosinacids, which has been subjected to the Hyex" treatment either before,during, or after the esterification reaction and A is a group derivedfrom' an alcohol. The ethers, in accordance with this invention,.arecompounds having the following formula:

in which the R and A have the same meaning as in the formula. given forthe esters. The hydrocarbons, in accordance with this'invention, are thehydrocarbon nuclei of the isomeric rosin acids which have been subjectedto the Hyex" treatment and from which the carboxyl group has beenremoved. Such Hyex" Rosiny hydrocarbons may be produced by subjectingrosin or a rosin acid to the Hyex" treatment and then treating theresulting Hyex" rosin or Hyex" rosin. acid to remove the carboxyl group.Alternately the rosin or rosin acid may be decarboxylated, by treatmentwith a sulfonic acid reagent known to produce the decarboxylation ofrosin, and the resulting hydrocarbon then subjected to the Hyex"treatment. The salts, in accordance with this invention, are metallicsalts of a Hyex" rosin or "Hyex rosin acid. Such salts will desirably beproduced by subjecting the rosin or rosin acid to the Hyex treatment andthen forming the salt by reaction with a suitable metallic compound,such as, for example, the metallic hydroxide. Alternately, but lessdesirable, the rosin or rosin acid may be treated with a suitablemetallic com! pound to form the salt, and this salt then subjected tothe Hyex" treatment.

The following examples further illustrate the process and products inaccordance with my invention.

2,180,997 with respect to the functional group, but different EXAMPLE 'IPan aea-non or Hrnx Ms'rm Amn'rs'm Methyl abietate was contacted withthe palladium supported on granular alumina described hertofore, at atemperature of 230 C. and for a period of 80 minutes. Table I gives acomparison of the' properties of methyl abietate after this treatment,with those of the original methyl abietate.

Table I Methyl abietate Hyex methyl (before treatment) abietete'lhiocysnate number..- 4.1. Physical condition at room Liquid Pastycrystals.

temperature.

Color Greenish-yellow... Colorless. Methoxyl (CH:O) 9.7%. 9.6%.

The comparisons shown in the above table demonstate that the Hyextreatment has practically eliminated the unsaturation of the methylabietate as measured by the thiocyanate value,

increased its melting point, reduced its color, and

had practically no eflect on the extent of its esteriflcation.

The following example in which 1" wood rosin is subjected simultaneouslyto the Hyex reaction and to esterification illustrates the second of thethree alternate embodiments of this invent on.

- EXAMPLE II Pimmaa'rron or Hrsx Ma'rnrnhnmrs'rn Table II "I" wood rosinHyex" methyl (untreated) sbietate Thiocyanate value a e. Acid number 16965. Methoxy content. 0.2%. 6.3%.

EXAMPLE HI Paarsas'rion on THE Srnsnrr. Earns or Hrnx Amnucan GUM RosinThirty g. of "Hyex" American gum rosin produced by subjecting Americangum rosin to the Hyezr' reaction was admixed with 24 g. of stearylalcohol. This mixture was then heated at a temperature of 200 C. in acurrent of car bon dioxide for a period of 20 hours. At the end' of thistime it was found that the acid number Percent 10 Acid number 1.5

Hydroxyl content 1.9 Ester content 70 EXAMPLEIV Pmansrrorz or Gmrczaor.Es'rna or Ammrcan GUM ROSIN 25 A mixture of 12.5 parts of glycerol and100 parts of "Hyex" American gum rosin produced by subjecting Americangum rosin to the Hyex reaction was heated at 270 C. for a period of 8%hours in an atmosphere of carbon dioxide. .At the end of this period theexcess glycerine was removed from the reaction mixture by re- 'ducingthe pressure to 15 m. for hour at a temperature of 270 C. The remainingester was then cooled to 200 C. while still under vacuum, and thencooled further to room temperature under atmospheric pressure. Theproduct gave the following analyses:

Acid number 5 ,Melting point (drop method)- 96 C.

Color 80 ampere 41 red. Grade (U. 8. standard rosin types) E.

EXAMPLEV Pmm'rron. or Gnronaor. Esra-a or Famvcn GUM Rosm EXAMPLE VIPanrm'rion or HYEx WOOD ROSIN OIL Four hundred g. of the Hyex wood rosinproduced by subjecting wood rosin to the Hyex" reaction was heated to285 C. with of 1% by weight of paratoluene sulfonic acid. Thetemperature was then raised to 220 0., and maintained at this point for4 hours. This treatment produced 390 g. of a crude rosin an acid numberof 58 as compared with an acid number of 160 for the original Hyex" woodrosin. Substantially neutral oil was then produced by dissolving 150 g.of this crude oil in 200 g. of petroleum ether, washing this solutionwith an aqueous caustic soda solution, and evaporating thepetroleumether. Ninety-seven g. of

and washed free of died by an alternative melted at 185 v United Statesoil having 5 an oil having the following analyses was ob- -tained:

Acid'number 1.0 Refractive index at 20 C 1.5475

Thiocyanate value 40.5

A second portion or the crude rosin oil was puriprocedure as follows:

Fifteen g. of sodium carbonate and 25 g. of water was added to 150 g. ofthe crude oil. When the reaction was complete the mixture was heated andthe water evaporated. This product was then distilled under reducedpressure to give 80 g. of a pale rosin oil as a. distillate. This palerosin oil gave the following analyses:

Acid number 0.75 Refractive index at 20 C 1. 5543 Thiocyanate value 31.5

The fact that the changes in a Rosinyi compound caused by the Hyextreatment, in accordance with this invention, occur solely within thehydrocarbon nucleus derived from a rosin acid in the RosinyY compoundtreated, and that identical compounds can be produced by following thedifferent embodiments of the method in accordance with this invention,is strikingly demonstrated by the following experiment:

Abietic acid was given the Hyex treatment in accordance with thisinvention to produce a Hyex abietic acid. This product was thenesterified with methyl alcohol and the ester nitrated. The resultantcrystalline nitrate melted at 185 0. Pure methyl abietate, made fromuntreated abietic acid was then given the "Hyex treatment by the methodin accordance with this invention as shown in Example I, above, andsubsequently nitrated. This crystalline nitrate also 0., and a mixtureof this nitrate and the nitrate produced as described above meltedsharply at 185" C. The two nitrates are thus proved to be chemicallyidentical, which proves that the Hyex treatment in-accordance with thisinvention, affects only the hydrocarbon nucleus of the Rosinyl compound.

It will be understood that the details and examples hereinbefore setforth are illustrative only, and that the invention as herein broadlydescribed and claimed is in no way limited thereby.

It will be understood that the tenn "unsaturation" is used in thisspecification and in the appended claims to refer to the unsatisfiedcarbon valences of the type represented by a double bond in unsaturatedaliphatic compounds and conveniently measured by the thiocyanate value.This application is a division of my application for United StatesLetters Patent, Serial No. 84,877, filed June 12, 1936, which is in turna continuation-in-part of my applica ion for Letters Patent, Serial No.6,403, filed February 13, 1935.

What I claim and desire to protect by Letters Patent is: I 1. A compoundof the formula in which R isthe hydrocarbon nucleus of an acid of thegroup consisting of rosins, rosin acids, partially hydrogenated resins,and partially hydrogenated rosin acids, which has been treated with ahydrogenation catalyst in the absence of any added substance capable ofreducing the unsaturation of the hydrocarbon nucleus under theconditions of treatment, and A is a hydrocarbon radical of an aliphatic,aromatic or hydroaromatic alcohol, the said compound being characterizedby the fact that it' has a lesser degree of unsaturation than that 01asimilar compound in which R is untreated.

2 A compound of the formula in which R. is the hydrocarbon nucleus of arosin acid which has been treated with a hydrogenation catalyst in theabsence of any added substance capable of reducing the unsaturation ofthe hydrocarbon nucleus under the conditions of treat-v ment, and A is ahydrocarbon radical of an all phatic, aromatic or hydroaromatic alcohol,the said compound being characterized by the fact that it has a lesserdegree of unsaturation than that or a similar compound in which R isuntreated.

3. A compound of the formula R-COO-A in which R is the hydrocarbonnucleus. of a resinacid which has been treated with a hydrogenationcatalyst in the absence 01 any added substance capable of reducing theunsaturation of the hydrocarbon nucleus under the conditions oftreatment, and A is a hydrocarbon radical of an aliphatic alcohol, thesaid compound being characterized by the fact that it has a lesserdegree of unsaturation than that of a similar compound in which R isuntreated.

4. A product formed by treating a monohydric alcohol ester of a rosinwith a hydrogenation catalyst in the absence of added substances capableof reducing the unsaturation of the material under the conditions oftreatment, said product being characterized by the fact that it has alesser degree of unsaturation than the material from which it wasformed.

5. A product formed by treating a polyhydric alcohol ester or a rosinwith a hydrogenation catalyst in the absence or added substances capableof reducing the unsaturation oi the material under the conditions oftreatment, said product being characterized by the fact that it has alesserdegree of, unsaturation than the material from which it wasformed. 6. A product formed by treating a monohydric alcohol'ester orwood rosin with a hydrogenation catalyst in the absence of addedsubstances capable of reducing the unsaturation of the material underthe conditions of treatment, said product being characterized by thefact that it has a lessor degree of unsaturation than the material fromwhich it was formed.

"I. A product formed by treating a polyhydric alcohol ester or woodrosin with a-hydrogenation catalyst in the absence of addedsubstancescapable or reducing the unsaturation of the material under theconditions of treatment, said product being characterized by the factthat it has a lesser degree of unsaturation than the material from whichit was formed.

8. A product formed by treating glycerol abletate with a hydrogenationcatalyst in the absence of added substances capable of reducing theunsaturation of the material under the conditions or treatment, saidproduct being characterized by the fact that it has a lesser degree ofunsaturation than the material from which it was formed.

9. A product formed by treating methyl abletate with a hydrogenationcatalyst in the absence of added substances capable of reducing theunsaturation oi the material under the conditions of treatment, saidproduct being characterized by the fact that it has a lesser degree ofunsaturation than the material from which it was formed.

10. The method of treating a rosin ester which includes contacting arosin ester with a hydrogenation catalyst in the absence of addedsubstances capable of reducing the unsaturation of the rosin esterwhereby the unsaturation of the rosin ester is reduced.

11. The method of treating a rosin ester which includes heating a rosinester with a hydrogenation catalyst in the absence of added substancescapable oi reducing the unsaturation of the rosin ester whereby theunsaturation of the rosin ester is reduced.

12. The method of treating a rosin ester which includes heating a rosinester with a. hydrogenation catalyst at a temperature within the rangeof about 150 C. to about 250 C. in the absence of added substancescapable of reducing the unsaturation of the rosin ester whereby theunsaturation of the rosin ester is reduced.

13. The method of treating a rosin ester which includes contacting arosin ester with a noble metal hydrogenation catalyst in the absence ofadded substances capable of reducing the unsaturation of the rosinester.

14. The method of treating a rosin ester which includes contacting arosin ester with a base metal hydrogenation catalyst in the absence ofadded substances capable of reducing the unsaturation of 'the rosinester whereby the unsaturation of the rosin ester is reduced.

15. The method of treating a rosin ester which includes contacting arosin ester with a palladium hydrogenation catalyst in the absence ofadded substances capable of reducing the unsaturation or the rosinester.

16. The method of treating a rosin ester which includes contacting arosin ester with a catalyst comprising palladium lar alumina in theabsence of added substances carable of reducing the unsaturation oftherosin es er.

. 1'7. The method of treating a rosin ester which includes contacting arosin ester at an elevated temperature and in liquid phase with ahydrogenation catalyst in the absence of added substances capable ofreducing the unsaturation of the rosin ester whereby the unsaturationof, the rosin ester is reduced.

' 18. The method of treating a rosin ester which includes contacting arosin ester with a noble metal hydrogenation catalyst at a temperaturewithin the range of about 150 C. to about 250 C, in the absence of addedsubstances capable of reducing the unsaturation of the rosin ester.

' 19. The method of treating a rosin ester which includes contacting arosin ester at an elevated temperature and in liquid phase with a nickelhydrogenation catalyst in the absence of added substances capable oireducing the unsaturation of the rosin ester.

20. The method of treating a rosin ester which includes contacting arosin ester in liquid phase and at an elevated temperature with acatalyst comprising palladium black supported on granular alumina, inthe absence of added substances cagable of reducing the unsaturation ofthe rosin es er.

EDWIN R.

black supported on granu-

